US4205124A - Low gamma photographic developer - Google Patents

Low gamma photographic developer Download PDF

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Publication number
US4205124A
US4205124A US06/003,056 US305679A US4205124A US 4205124 A US4205124 A US 4205124A US 305679 A US305679 A US 305679A US 4205124 A US4205124 A US 4205124A
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grams
developer
composition
gamma
hydroquinone
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US06/003,056
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Harvey A. Hodes
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US Air Force
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US Air Force
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers

Definitions

  • This invention relates to a low gamma photographic developer for the rapid processing of aerial film.
  • low gamma photographic developers result in certain advantages in aerial surveillance. Included among the advantages are simplification of camera design since the need for automatic exposure control is greatly reduced, reduction in overexposure errors, and compression of the density range of the negative to fit the density range of the positive image to be produced. From a practical standpoint, the choice between high or low contrast aerial photography is dependent upon the particular situation and the information desired. At high altitude, a high contrast (high gamma) developer is needed to detect small variations in luminance and to compensate for scattering and flare. At low and medium altitudes, the fundamental advantages of low contrast (low gamma) developers are increased resolution due to finer grain development and a wider exposure latitude. Since aerial reconnaissance is in many instances concerned with low and medium latitude photography, there is a real need for an improved low gamma developer.
  • a developer formulation contains three developing agents, namely, 3-pyrazolidones (Phenidone), dihydroxybenzenes (hydroquinone), and enediols.
  • the amount by weight of hydroquinone used is more than ten times the amount of Phenidone.
  • Such a high weight ratio of hydroquinone to Phenidone is incapable of providing a low gamma photographic developer.
  • Another object of the invention is to provide a low gamma photographic developer which is especially adapted for the rapid processing of aerial film.
  • the present invention resides in the discovery that a 1 to 2 weight ratio of 1-phenyl-3-pyrazolidone (Phenidone) to hydroquinone is critical in providing a low gamma developer composition.
  • the actual amounts of the aforementioned developing agents used depends upon the volume of the developer composition that is formulated.
  • the developer composition of this invention comprises 1 gram of Phenidone, 2 grams of hydroquinone, and sufficient water to make one liter, the composition having a gamma less than one and a pH ranging from about 9.8 to 10.4.
  • the gamma value of the composition usually ranges from about 0.35 to 0.95 while the pH of the composition is preferably in the range of about 10.2 to 10.4.
  • Use of the developer composition makes it possible to obtain unexpectedly improved film processing rates.
  • the developer is stable at elevated temperatures for extended periods of time.
  • the present invention resides in a developer composition having a pH in the range of 10.2 to 10.4 and comprising the following ingredients in the amounts indicated per liter of composition:
  • the Phenidone and hydroquinone in the critical 1 to 2 weight ratio functions as developing agents.
  • the composition is further characterized by the low concentration of the developer moiety.
  • the sodium carbonate acts as a pH buffering agent while the sodium sulfite is a preservative agent for the developers.
  • the formulation is particularly adapted for use in conventional processing, employing a stop bath and fix.
  • Each of the developer compositions contain sufficient water to make one liter.
  • Formulation A has a pH of 10.2 to 10.4 while the pH of formulation B is from 9.8 to 10.0.
  • the ingredients in the formulations common to those of the formulation set forth in the preceding paragraph perform the same function as indicated in that paragraph.
  • the polyethylene oxide serves a dual role, primarily as a development accelerator and secondarily as a protective colloid to reduce the adherence of sludge to processor walls.
  • the sodium thiosulfate is the conventional silver complexing agent in monobath formulations.
  • cysteine hydrochloride is another complexing agent which has the advantage of minimal sludge formation so that it is unnecessary to include the polyethylene oxide used in formulation A.
  • cysteine hydrochloride is an acid, it is necessary to increase the quantity of sodium carbonate to neutralize the acid and obtain the equivalent buffering capacity as in the other formulation.
  • a control run was also carried out under the same conditions, using Kodak MX 641 developer.
  • Example II A test was conducted to determine the storage stability of the dry ingredients of the developer composition described in Example I when stored in a stoppered glass vial.
  • the vial containing the ingredients was stored for 16 hours at 160° F., conditions comparable to those encountered in the storage of photographic equipment in the most severe desert environment. No change in gamma or speed was detected in a developer solution made from the packaged ingredients.
  • Example III A series of runs was carried out in which the developer formulation described in Example I was used to develop various films in a hand processing operation.
  • the films processed, the conditions used, and the results obtained are shown below in Table III.
  • the present invention provides a low gamma photographic developer which is eminently suitable for the rapid processing of aerial film.
  • the developer composition is further characterized by being stable to oxidative degradation.

Abstract

A photographic developer composition containing Phenidone and hydroquinone in a 1 to 2 weight ratio, the composition having a gamma less than 1 and a pH in the range of about 9.8 to 10.4. The composition is particularly useful as an extended range developer for rapid processing of aerial film.

Description

RIGHTS OF THE GOVERNMENT
The invention described herein may be manufactured or used by or for the government of the United States for all governmental purposes without the payment of any royalty.
This is a continuation, of application Ser. No. 876,444, filed Feb. 9, 1978, now abandoned.
FIELD OF THE INVENTION
This invention relates to a low gamma photographic developer for the rapid processing of aerial film.
BACKGROUND OF THE INVENTION
It is well known that use of low gamma photographic developers result in certain advantages in aerial surveillance. Included among the advantages are simplification of camera design since the need for automatic exposure control is greatly reduced, reduction in overexposure errors, and compression of the density range of the negative to fit the density range of the positive image to be produced. From a practical standpoint, the choice between high or low contrast aerial photography is dependent upon the particular situation and the information desired. At high altitude, a high contrast (high gamma) developer is needed to detect small variations in luminance and to compensate for scattering and flare. At low and medium altitudes, the fundamental advantages of low contrast (low gamma) developers are increased resolution due to finer grain development and a wider exposure latitude. Since aerial reconnaissance is in many instances concerned with low and medium latitude photography, there is a real need for an improved low gamma developer.
The patent literature is replete with disclosures of formulations for use as photographic developers. Examples of such patents include U.S. Pat. Nos. 3,804,624 and 3,865,591. These patents are considered to be pertinent to the invention disclosed herein since they describe formulations containing Phenidone (1-phenyl-3-pyrazolidone) and hydroquinone, ingredients of the developer composition of this invention. However, according to U.S. Pat. No. 3,804,624, addition of Phenidone to silver halide emulsions was unsuccessful since the accelerator compound is very susceptible to oxidation. In U.S. Pat. No. 3,865,591, a developer formulation is disclosed that contains three developing agents, namely, 3-pyrazolidones (Phenidone), dihydroxybenzenes (hydroquinone), and enediols. In examples of the patent, formulations are disclosed in which the amount by weight of hydroquinone used is more than ten times the amount of Phenidone. Such a high weight ratio of hydroquinone to Phenidone is incapable of providing a low gamma photographic developer.
It is a principal object of this invention, therefore to provide an oxidatively stable, low gamma photographic developer.
Another object of the invention is to provide a low gamma photographic developer which is especially adapted for the rapid processing of aerial film.
Other objects and advantages of the invention will become apparent to those skilled in the art upon consideration of the accompanying disclosure.
SUMMARY OF THE INVENTION
The present invention resides in the discovery that a 1 to 2 weight ratio of 1-phenyl-3-pyrazolidone (Phenidone) to hydroquinone is critical in providing a low gamma developer composition. The actual amounts of the aforementioned developing agents used depends upon the volume of the developer composition that is formulated. Thus, the developer composition of this invention comprises 1 gram of Phenidone, 2 grams of hydroquinone, and sufficient water to make one liter, the composition having a gamma less than one and a pH ranging from about 9.8 to 10.4. The gamma value of the composition usually ranges from about 0.35 to 0.95 while the pH of the composition is preferably in the range of about 10.2 to 10.4. Use of the developer composition makes it possible to obtain unexpectedly improved film processing rates. Furthermore, the developer is stable at elevated temperatures for extended periods of time.
In one embodiment, the present invention resides in a developer composition having a pH in the range of 10.2 to 10.4 and comprising the following ingredients in the amounts indicated per liter of composition:
Phenidone--1 gram
Hydroquinone--2 grams
Sodium Carbonate--10 grams
Sodium Sulfite--30 grams
In the foregoing developer composition, the Phenidone and hydroquinone in the critical 1 to 2 weight ratio functions as developing agents. The composition is further characterized by the low concentration of the developer moiety. The sodium carbonate acts as a pH buffering agent while the sodium sulfite is a preservative agent for the developers. The formulation is particularly adapted for use in conventional processing, employing a stop bath and fix.
The following are variations of the above formulation, (designated A and B) that are readily adapted to monobath processing:
______________________________________                                    
               A         B                                                
______________________________________                                    
Phenidone         1 gram      1 gram                                      
Hydroquinone      2 grams     2 grams                                     
Sodium Carbonate 10 grams    40 grams                                     
Sodium Sulfite   30 grams    30 grams                                     
Sodium Thiosulfate                                                        
                 50 grams    --                                           
Polyethylene oxide                                                        
                  4 grams    --                                           
Cysteine hydrochloride                                                    
                 --          10 grams                                     
______________________________________
Each of the developer compositions contain sufficient water to make one liter. Formulation A has a pH of 10.2 to 10.4 while the pH of formulation B is from 9.8 to 10.0. The ingredients in the formulations common to those of the formulation set forth in the preceding paragraph perform the same function as indicated in that paragraph. In formulation A the polyethylene oxide serves a dual role, primarily as a development accelerator and secondarily as a protective colloid to reduce the adherence of sludge to processor walls. The sodium thiosulfate is the conventional silver complexing agent in monobath formulations. In formulation B the cysteine hydrochloride is another complexing agent which has the advantage of minimal sludge formation so that it is unnecessary to include the polyethylene oxide used in formulation A. However, since cysteine hydrochloride is an acid, it is necessary to increase the quantity of sodium carbonate to neutralize the acid and obtain the equivalent buffering capacity as in the other formulation.
A more comprehensive understanding of the invention can be obtained by referring to the following illustrative examples which are not intended, however, to be unduly limitative of the invention.
EXAMPLE I
A run was conducted in which Plus X Aerographic 2402 film was processed in Kodak Versamat processor, model 5A-N. The following developer composition of this invention was utilized: p1 Phenidone--1 gram
Hydroquinone--2 grams
Sodium Carbonate--10 grams
Sodium Sulfite--30 grams
Water to make 1 liter
pH--10.2-10.4
A control run was also carried out under the same conditions, using Kodak MX 641 developer.
The results obtained in the run are shown below in Table I.
              TABLE I                                                     
______________________________________                                    
           Invention Run                                                  
                       Control Run                                        
______________________________________                                    
Temp., ° C.                                                        
             35            35                                             
Fog level    0.08          0.08                                           
Gamma        0.55          1.55                                           
Speed.sup.(1)                                                             
             160           160                                            
Processing rate,                                                          
ft/min       15            3.5                                            
______________________________________                                    
 .sup.(1) Effective aerial film speed (EAFS) per ANSI PH 2.34 1969 for the
 processing conditions described in this publication.
From the foregoing data, it is seen that the processing rate when using the low gamma developer of this invention is nearly five times greater than that obtained with a commercially available developer. This increase in processing rate represents an important and unexpected improvement in the use of the present developer.
EXAMPLE II
A run was conducted to test the stability of the developer composition described in Example I in the Versamat processor. The results obtained originally and after 5 days exposure to air are shown below in Table II.
              TABLE II                                                    
______________________________________                                    
           Original   After 5 days                                        
______________________________________                                    
Fog level    0.08         0.08                                            
Gamma        0.62         0.53                                            
Speed        125          125                                             
pH           10.2         10.15                                           
______________________________________
The data in the above table demonstrate that the developer composition of this invention is oxidatively stable over an extended period of time. Of particular significance is the fact that there was a slight drop in gamma, i.e., from 0.62 to 0.52, even after the five day exposure to air.
EXAMPLE III
A test was conducted to determine the storage stability of the dry ingredients of the developer composition described in Example I when stored in a stoppered glass vial. The vial containing the ingredients was stored for 16 hours at 160° F., conditions comparable to those encountered in the storage of photographic equipment in the most severe desert environment. No change in gamma or speed was detected in a developer solution made from the packaged ingredients.
EXAMPLE IV
A series of runs was carried out in which the developer formulation described in Example I was used to develop various films in a hand processing operation. The films processed, the conditions used, and the results obtained are shown below in Table III.
              TABLE III                                                   
______________________________________                                    
Film     Temp. ° C.                                                
                   Time, sec.                                             
                            Gamma  Speed  Fog                             
______________________________________                                    
Tri X aero-                                                               
         26.5      30       0.38   300-160                                
                                          0.14                            
graphite 2403                                                             
         35        15       0.35   320-250                                
                                          0.14                            
Plus X   26.5      30       0.32   125    0.34                            
Pan 5062 35        15       0.35   160    0.34                            
         35        30       0.60   200    0.40                            
Panatomic X                                                               
         26.5      30       1.0    40     0.08                            
Aerial 3400                                                               
         15        0.65     25     0.10                                   
         35        10       0.83   50     0.10                            
         35        15       0.88   50     0.10                            
         35        30       1.78   40     0.12                            
Panatomic X                                                               
         26.5      30       0.58   50     0.30                            
5060     35        15       0.48   64-50  0.26                            
         35        30       0.85   100    0.32                            
Plux X Aero-                                                              
graphic 2402                                                              
         35        30       0.60   160-125                                
                                          0.10                            
______________________________________
EXAMPLE V
A series of runs was conducted in which various films were hand processed in a thiosulfate monobath. The following is the developer composition utilized in the runs:
Phenidone--1 gram
Hydroquinone--2 grams
Sodium Carbonate--10 grams
Sodium Sulfite--30 grams
Sodium Thiosulfate--50 grams
Polyethylene oxide grade 4000--4 grams
Water to make 1 liter
pH 10.2-10.4
The films processed, the conditions used, and the results obtained are shown below in Table IV.
              TABLE IV                                                    
______________________________________                                    
Film      Temp, ° C.                                               
                    Time,min Gamma  Speed Fog                             
______________________________________                                    
Tri X Aerogra-                                                            
          26.5      4.0      0.66   200   0.16                            
phic 2403 35        3.0      0.90   320   0.24                            
Plus X    26.5      3.5      0.48   100   0.32                            
Pan 5062  35        2.5      0.73   160   0.34                            
Panatomic X                                                               
          26.5      1.5      0.68    32   0.08                            
Aerial 3400                                                               
          35        1.0      1.0    100   0.10                            
Panatomic X                                                               
          26.5      2.0      0.45    10   0.34                            
5060      35        1.5      0.64    40   0.32                            
______________________________________
EXAMPLE VI
A series of runs was carried out in which various films were hand processed in a cysteine monobath. The following is the developer composition employed in the runs:
Phenidone--1 gram
Hydroquinone--2 grams
Sodium Carbonate--40 grams
Sodium Sulfite--30 grams
Cysteine Hydrochloride--10 grams
Water to make 1 liter
pH 9.8-10.0
The films processed, the conditions used, and the results obtained are set forth below in Table V.
              TABLE V                                                     
______________________________________                                    
                              Gam-                                        
Film       Temp, ° C.                                              
                     Time,min ma    Speed Fog                             
______________________________________                                    
Tri X Aerogra-                                                            
           26.5      5.0      0.62  320   0.18                            
phic 2403  35        3.5      0.73  500   0.22                            
Plus X Pan 502                                                            
           35        3.5      0.40  50    0.30                            
           26.5      2.5      0.63  125   0.30                            
Panatomic X                                                               
           26.5      1.5      0.69  12    0.06                            
Aerial 3400                                                               
           35        1.0      0.78  40    0.08                            
Panatomic X 5060                                                          
           2.0       0.32     12    0.32                                  
           35        1.5      0.48  40    0.30                            
Plus X Aerogra-                                                           
           26.5      3.5      0.56  80-64 0.06                            
phic 2402  35        3.0      0.72  160   0.06                            
______________________________________
As seen from the foregoing, the present invention provides a low gamma photographic developer which is eminently suitable for the rapid processing of aerial film. The developer composition is further characterized by being stable to oxidative degradation.
As will be evident to those skilled in the art, modifications of the present invention can be made in view of the foregoing disclosure without departing from the spirit and scope of the invention.

Claims (4)

I claim:
1. A photographic developer composition for processing aerial-type film to a gamma less than 1, said composition consisting of 1 gram of 1-phenyl-3-pyrazolidone and 2 grams of hydroquinone as the sole developing agents, and sufficient water to make one liter, the composition also contains sufficient alkali to provide a pH ranging from about 9.8 to 10.4.
2. The composition according to claim 1 which further contains 10 grams of sodium carbonate and 30 grams of sodium sulfite and has a pH ranging from about 10.2 to 10.4.
3. The composition according to claim 1 which further contains 10 grams of sodium carbonate, 30 grams of sodium sulfite, 50 grams of sodium thiosulfate and 4 grams of polyethylene oxide and has a pH ranging from about 10.2 to 10.4.
4. The composition according to claim 1 which further contains 40 grams of sodium carbonate, 30 grams of sodium sulfite and 10 grams of cysteine hydrochloride and has a pH ranging from about 9.8 to 10.0.
US06/003,056 1978-02-09 1979-01-12 Low gamma photographic developer Expired - Lifetime US4205124A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1054295A1 (en) * 1999-05-18 2000-11-22 Eastman Kodak Company Developing/fixing monobath and its use for processing low silver black-and-white photographic elements

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB906034A (en) * 1957-10-29 1962-09-19 Cormac Chemical Corp Photographic developing and fixing composition and process
US3573912A (en) * 1964-08-03 1971-04-06 Bell & Howell Co Stabilization of silver halide printout recording papers
US3615513A (en) * 1965-11-01 1971-10-26 Eastman Kodak Co Inhibition of silvering in photographic processing solutions
US3632341A (en) * 1970-03-13 1972-01-04 Itek Corp Photographic developer
US3772019A (en) * 1972-05-19 1973-11-13 H & W Co Inc St Johnsbury Novel developer and process
US3839046A (en) * 1972-10-12 1974-10-01 Ilford Ltd Process for the production of a photographic print
US3870479A (en) * 1971-10-15 1975-03-11 Fuji Photo Film Co Ltd Lithographic type diffusion transfer developer

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB906034A (en) * 1957-10-29 1962-09-19 Cormac Chemical Corp Photographic developing and fixing composition and process
US3573912A (en) * 1964-08-03 1971-04-06 Bell & Howell Co Stabilization of silver halide printout recording papers
US3615513A (en) * 1965-11-01 1971-10-26 Eastman Kodak Co Inhibition of silvering in photographic processing solutions
US3632341A (en) * 1970-03-13 1972-01-04 Itek Corp Photographic developer
US3870479A (en) * 1971-10-15 1975-03-11 Fuji Photo Film Co Ltd Lithographic type diffusion transfer developer
US3772019A (en) * 1972-05-19 1973-11-13 H & W Co Inc St Johnsbury Novel developer and process
US3839046A (en) * 1972-10-12 1974-10-01 Ilford Ltd Process for the production of a photographic print

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Mason, Photographic Processing Chemistry, 1975, pp. 42-43. *
Zonars, "New Low-Contrast Developer for Rapid Processing of Aerial and Duplicating Films", Jul. 1963. *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1054295A1 (en) * 1999-05-18 2000-11-22 Eastman Kodak Company Developing/fixing monobath and its use for processing low silver black-and-white photographic elements

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